N-cycloalkyl anilines



United States Patent Oifice 3,546,295 N-CYCLOALKYL ANILINES Lester L. Maravetz, Westfield, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Aug. 1, 1968, Ser. No. 749,326 Int. Cl. C07c 87/34, 121/52, 143/38 U.S. Cl. 260577 13 Claims ABSTRACT OF THE DISCLOSURE Cycloalkane derivatives of nitrated aryl compounds useful as herbicides, such as those, e.g., of the general formula R1IITR2 wherein (1) R is a cycloalkyl containing group characterized by the following structural formula in which the cycloalkyl ring itself may be optionally substituted with C C alkyl or C -C alkenyl; n is either or 1; m is a positive integer ranging from 2 to 4 when n is 1, however when n is 0, m is 2; (2) R is C -C straight or branched chain alkyl, C -C alkenyl, cyclopropyl, C cycloalkylalkyl or C -C alkylmercaptoalkyl; (3) R is hydrogen or N0 (4) R is hydrogen, C -C alkyl, CF CH S(O) C H S(O) or C H S(O) wherein at is 0, 1 or 2. Exemplary of an especially preferred nitrated aryl cyclopropane derivative is the compound of the formula FIELD OF THE INVENTION This invention relates to novel cycloalkane derivatives of nitrated aryl compounds and their use as pesticides. More particularly, this invention relates to novel cycloalkane derivatives of nitrated aryl compounds, formulations or compositions thereof, and their use as herbicides.

PRIOR ART Alkyl derivatives of nitrated aryl compounds and their use as herbicides are well known in the art. For example, N,N-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline, a commercial herbicide known in the art as Treflan, is disclosed in US. Pat. 3,257,190.

Moreover, sulfanilamides of the structure are disclosed in US. Pat. 3,367,949, but such sulfanilamides have not become, or been suggested as, successful commercial herbicides;

3,546,295 Patented Dec. 8, 1970 None of the prior art, therefore, has disclosed or sug gested the compounds presented in this invention, nor been cognizant of the benefits in biological activity to be gained by utilization of such compounds in pesticidal, particularly herbicidal, applications.

SUMMARY OF THE INVENTION In general, the cycloalkane derivatives of nitrated aryl compounds of this invention are characterized by the formula wherein (1) R is a cycloalkyl containing group characterized by the following structural formula in which the cycloalkyl ring itself may be optional substituted with C C alkyl or C -C alkenyl; n is either 0 or 1; m is a positive integer ranging from 2 to 4 when n is 1, however when n is 0, m is 2; (2) R is C -C straight or branched chain alkyl, C -C alkenyl, cyclopropyl, C cycloalkylalkyl or C -C alkylmercaptoalkyl; (3) R is hydrogen or N0 (4) R is hydrogen, C -C alkyl, CF CH S(O) C H S(O) or C3H7S(O) wherein x is O, 1 or 2. Exemplary of an especially preferred nitrated aryl cyclopropane derivative is the compound of the formula The foregoing compounds can be readily prepared by the following synthetic methods. For example, the preferred method for preparation of these products comprises reaction of the highly reactive compound 3,5-dinitro-4-chlorobenzotrifiuoride with an amine of the general structure R R NH, where R and R can have the same designation as previously expressed above. During this reaction, elimination of hydrogen chloride occurs and this reacts with excess of the amine R R NI-I to form the corresponding amine hydrochloride salt; alternatively, if desired, any tertiary amine, such as dimethylaniline or triethylamine can be reacted with the eliminated HCl to form the corresponding amine hydrochloride salt.

If it is desired that a suitable organic solvent such as ether, benzene, toluene, hexane, chlorinated hydrocarbons, etc., be used in this method, the resulting amine hydrochloride, which is insoluble in such solvent, is ordinarily removed by filtration. The filtrate, upon removal of the solvent, yields the desired product.

In an alternative embodiment, the novel amines of this invention can themselves be prepared via a two-step process in which the first step involves the reaction of a cycloalkyl carbonylchloride with various types of primary amines to form the corresponding N-substituted cycl0 alkanecarboxamide. In the second step of this alternative embodiment, these amides are then reduced to the desired secondary amines with an appropriate reducing agent, such as lithium aluminum hydride, or diborane, for example.

Typical illustrative reactants employed for the prepounds embraced by the previous general formula on ferred method of this invention include, e.g., amines pages 4 and 8 in lude, but by no means exhaustively: such as N-cyclopropyl-methyl-N-n-propylamine; N-cyelopropylmethyl-N-methyl-4-trifluoromethyl- N-cyclopropylmethyl-N-ethylamine, 2,6-dinitroaniline; N-cyclopropyl-methyl-N-n-butylamine; N-cyclopropylmethyl-N-ethyl-4-trifiuoromethyl- N-cyclohexyl-N-methylamine; 2,6-dinitroaniline; N-cyclopentylmethyl-N-ethylamine; N-cyclopropylmethyl-N-n-propyl-4-trifluoromethyl- N-cyclobutylmethyl-N-ethylamine; etc.; with any of the 2,6-dinitroani1ine; following: N-cyclopropylmethyl-N-isopropyl-4-trifluoromethyl- 3,S-dinitro-4-chlor0benzotrifluoride; 10 2,6-dinitroaniline; 4-chloro-3,S-dinitrophenyl methylsulfone; N-cyclopropylmethyl-N-n-butyl-4-trifiuoromethyl- 1-chloro-2,6-dinitrobenzene; 2,6-dinitroaniline; 3 ,5 -dinitro-4-chlorotolucne; N-cyclopropylmethyl-N-(3-methylmercaptopropyl)-4- 4-ehloro-3 ,S-dinitrobenzonitrile; trifluoromethyl-2,6-dinitroaniline; 4-chloro-3 -m'tro-benzotrifluoride; etc. 19 N,N-bis(cyclopropylmethyl)-4-trifluoromethyl- The typical reaction conditions for the alternative meth- 2,6-dinitroaniline; ods of preparing the compounds of this invention are 4-(methylsulfonyl)-2,6-dinitro-N-cyclopropylmethyl-N- tabulated in Table I below: methylaniline;

TABLE I Typical Reaction Conditions for Preparation of N-Cyclopropylmethyl-N-n-Propyl-4-Triiluoromethyl-2,6Dinitroaniline Would Include- Single step reaction Molar ratio of reactants Temperature, C. P. Atm. Preferred solvents Undesirablc solvents 3,5-dinitro-4-chlorobenzotrifiuoride (1 mole) plus N- 0 C.-150 C 1 atm-.. Benzene, toluene, etheis,

cyclopropylmethyLN-n-propyl amine (1.1 moles) plus alcohols, chlorinated triethyl amine (1.1-2.0 moles). hydrocarbons.

Typical Reaction Conditions for Preparation of .Amincs Would Include- Two-step reaction Molar ratio of reactants Temperature, C. P. Atm. Preferred solvents Undesirable solvents Step (a) Cyelopropanecarboxylic acid chloride (1 mole) 10 C. to 100 C- 1 atm-.. Benzene, toluene, ethers, Alcohols, water.

plus mpropylamine (2.1-3.0 moles). chlgrinated hydroear ons. Step (b) N-n-propylcyclopropanecarboxamide (1.0 mole) C. to 75 0...- 1 atm. Diethylether, tetrahydro- Aqueous or alcoholic solvents.

plus lithium aluminum hydride (1.1-2.0 moles). iuran, benzene.

The preferred nitrated aryl cyclopropane derivatives of 4-(methylsulfonyD-2,6-dinitro-N-cyclopropylmethyl-N- this invention are characterized by the following formula: ethylaniline;

4-(methylsulfonyD-Z,6-dinitro-N-cyclopropylmethyl-N-nk 'oH2N"-Rl propylaniline;

I 4-(methylsulfonyl)-2,6-dinitro-N-cyclopropylmethyl-N-n- O2N- -NOz butylaniline;

' 4-(methylsulfonyl)-2,6-dinitro-N-cyclopropylmethyl-N- (3-methylmercapto-propyl)aniline;

I N-cyclopropylmethyl-N-n-propyl-2,6-dinitroaniline;

R2 N-cyclopropylmethyl-N-ethyl-2,6-dinitroaniline; where R can be hydrogen, methyl, ethyl, n-propyl, iso- Y P PY Y -P PY -P' propyl, n-butyl, sec-butyl, isobutyl, cyclopropylmethyl, y p py y y -pn-amyl, isoamyl, sec-amyl, allyl, propargyl, crotyl, N-cyclopropylmethyl-N-n-propyl-4-cyano-2,6-dinitromethallyl, methoxyethyl, ethoxyethyl, n-propoxyethyl, 2- aniline;

methoxyethyl, 2 ethoxyethyl, Z-methyhnercaptoethyl, 3- y P PY y -W methylmercaptopropyl, trifluoromethyl, pentafiuoroethyl, N-cyclopropylmethyl-N-n-propyl-2-nitro-4-trifluoro- 3-chloropropyl, trichloromethyl, bromomethyl, etc.; and methyl-aniline;

R can be hydrogen, methyl, ethyl, n-propyl, isopropyl, N-cyclobutylmethyl-N-ethyl-4-trifluoromethyl-2,6- n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, di it o ili y y qp y Py y s s, phenyl and N-cyclopentylmethyl-N-ethyl-4-trifluoromethyl-2,6- phenyl substituted with alkyl, halogen, N0 etc. dinitroaniline;

R can also be a halogen such as chlorine, bromine or l h l th 1.N methyl-4-trifiuoromethyl-2 6- fluorine; haloalkyl groups such as trifluoromethyl, chlorodinitroaniline.

methyl, trichloromethyl, bromoethyl, chloroethyl, bromoethyl, chloropropyl, bromopropyl; and the like. Moreover, N-cyclohexybNfllethyl-4-mfiuoromethyla6dlmtro- R can be RS(O) where R=alkyl and x=0, 1, 2. aniline;

In still anothe: embodiment, R can also be a sulfon- 'ggyg fiiii g amide group such as SO NR R where R and R; can be hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, and R and 4(methylsu1fny1)'2=6'dlmtro'N'cyclopropyl'N'ethyl' R when taken together with the nitrogen atom to which aniline; they are attached can form a ring system such as aziridyl, W P PY y Y pyrrolidinyl, or piperidinyl, etc. aniline;

N-cyclopropyl-N-cyclopropylmethyl-4-trifluoromethyl- 2,6-dinitroaniline.

Nonlimiting, typical preferred nitrated aryl cyclopropane derivatives of this invention exemplary of com 'Of the foregoing preferred compounds, the most preferred compounds of this invention include:

N-cyclopropylmethyl-N-ethyl-4-trifluoromethyl- 2,6-dinitroanilinc; N-cyclopropylmethyl-N-n-propyl-4-trifluoromethyl- 2,6-dinitroanilinc; N-cyclopropylmethyl-N-n-butyl-4-trifluoromethyl- 2,6-dinitroaniline; N-N-bis(cyclopropylmethyl)-4-trifiuoromethyl- 2,6-dinitroaniline; 4-(methylsulfonyD-Z,6-dinitro-N-cyclopropylmethyl-N- ethylaniline; 4-(methylsulfonyl)-2,6-dinitro-N-cyclopropylmethyl-N-npropylaniline; 4-(methylsulfonyl)-2,6-dinitro-N-cyclopropylmethyl-N -11- butylaniline; N-cyclopropylmethyl-N-n-propyl-2,6-dinitroaniline; N-cyclopropylmethyl-N-n propyl-Z,6-dinitro-p-toluidine; N-cyclopropylmethyl-N-n-propyl-4-cyano-2,6-dinitroaniline; N-cyclopropylmethyl-N-ethyl-2,-dinitroaniline; N-cyclopropylmethyl-N-ethyl-2,6-dinitro-p-toluidine; N-cyclopropylmethyl-N-ethyl-4-cyano-2,G-dinitroaniline; N-cyclobutylmethyl-N-ethyl-4-trifluoromethyl- 2,6-dinitroaniline; 4-(methylsulfonyl)-2,6-dinitro-N-cyclopropyl-N ethylaniline; N-cyclopropyl-N-ethyl-4-trifluoromethyl-2,6-dinitroaniline; N-cyclopropyl-N-cyclopropylmethyl-4-trifluoromethyl- 2,6-dinitroaniline;

As previously noted, the present cycloalkane derivatives, and especially the cyclopropane derivative, of nitrated aryl compounds are useful as pesticides, particularly as herbicides. When so used, the biologically active cycloalkane derivatives of nitrated aryl compounds are preferably formulated with a suitable carrier or diluent or combinations thereof.

The term carrier or diluent as used herein means a material, which can be inorganic or organic and synthetic or of natural Origin, with which the active ingredient is mixed or formulated to facilitate its storage, transport, and handling and application to the plants to be treated. The carrier is preferably biologically and chemically inert and, as used, can be a solid or fluid. When solid carriers are used, they are preferably particulate. granular, or pelletized; however, other shapes and sizes of solid carrier can be employed as well. Such preferable solid carriers can be natural occurring minerals-although subsequently subjected to grinding, sieving, purification, and/ or other treatments-including, for example, gypsum; tripolite; diatomaceous earth; mineral silicates such as mica, vermiculite, talc, and pyrophyllite; clays of the montmorillonite, kaolinite, or attapulgite groups; calcium or magnesium limes, or calcite and dolomite; etc. Carriers produced synthetically, as for example, synthetic hydrated silica oxides and synthetic calcium silicates can also be used, and many proprietary products of this type are available commercially. The carrier can also be an elemental substance such as sulfur or carbon, preferably an activated carbon. If the carrier possesses intrinsic catalytic activity such that it would decompose the active ingredient, it is advantageous to incorporate a stabilizing agent, as for example, polyglycols such as diethylene glycol, to neutralize this activity and thereby prevent possible decomposition of the cycloalkane derivatives of the present nitrated aryl.

For some purposes, a resinous or waxy carrier can be used, preferably one which is solvent soluble or thermoplastic, including fusible. Examples of such carriers are natural or synthetic resins such as a coumarone resin, rosin, copal, shellac, dammar, polyvinyl chloride, styrene polymers and copolymers, a solid grade of polychlorophenol such as is available under the registered trademark Aroclor, a bitumen, an asphaltite, a wax for example beeswax or a mineral wax such as paraflin wax or montan wax, or a chlorinated mineral wax, or a microcrystalline wax such as those available under the registered trademark Mikrovan Wax. Compositions comprising such resinous or waxy carriers are preferably in granular or pelleted form.

Fluid carriers can be liquids, as for example, water, or an organic fluid, including a liquefied normally vaporous or gaseous material, or a vaporous or gaseous material, and can be solvents or nonsolvents for the active material. For example, the horticultural petroleum spray oils boiling in the range of from about 275 to about 575 F., or boiling in the range of about 575 to about 1,000 F. and having an unsulfonatable residue of at least about and preferably of at least about 90%, or mixtures of these two types of oil, are particularly suitable liquid carriers.

The carrier can be mixed or formulated with the active material during its manufacture or at any stage subsequently. The carrier can be mixed or formulated with the active material in any proportion depending on the nature of the carrier. One or more carriers, moreover, can be used in combination.

The compositions of this invention can be concentrates, suitable for storage or transport and containing, for ex ample, from about 5 to about 90% by weight of the active ingredient, preferably from about 20 to about wt. percent. These concentrates can be diluted with the same or different carrier to a concentration suitable for application. The compositions of this invention may also be dilute compositions suitable for application. In general, concentrations of about 0.1 to about 10% by weight, of active material based on the total weight of the composition are satisfactory, although lower and higher concentrations can'be applied if necessary.

The compositions of this invention can also be formulated as dusts. These comprise an intimate admixture of the active ingredient and a finely powdered solid carrier such as aforedescribed. The powdered carriers can be oiltreated to improve adhesion to the surface to which they are applied. These dusts can be concentrates, in which case a highly sorptive carrier is preferably used. These require dilution with the same or a diflerent finely powdered carrier, which can be of lower sorptive capacity, to a concentration suitable for application.

The compositions of the invention can be formulated as wettable powders comprising a major proportion of the active ingredient mixed with a dispersing, i.e., defiocculating or suspending, agent, and, if desired, a finely divided solid carrier and/or a wetting agent. The active ingredient can be in particulate form or adsorbed on the carrier and preferably constitutes at least about 10%, more preferably at least about 25%, by weight of the composition. The concentration of the dispersing agent should in general be between about 0.5 and about 5% by weight of the total composition, although larger or smaller amounts can be used if desired.

The dispersing agent used in the composition of this invention can be any substance having definite dispersing. i.e., defioccolating or suspending, properties as distinct from wetting properties, although these substances can also possess wetting properties as well.

The dispersant or dispersing agent used can be protective colloids such as gelatin, glue, casein, gums, or a synthetic polymeric material such as polyvinyl alcohol and methyl cellulose. Preferably, however, the dispersants or dispersing agents used are sodium or calcium salts of high molecular weight sulfonic acids, as for example, the sodium or calcium salts of lignin sulfonic acids derived from sulfite cellulose waste liquors. The calcium or sodium salts of condensed aryl sulfonic acid, for example, the products known as Tamol 731, are aslo suitable.

The wetting agents used can be non-ionic type surfactants, as for example, the condensation products of fatty acids containing at least 12, preferably 16 to 20, carbon atoms in the molecule, or abietic acid or naphthenic acid obtained in the refining of petroleum lubricating oil fractions with alkylene oxides such as ethylene oxide or pro pylene oxide, or with both ethylene oxide and propylene oxide, as, for example, the condensation product of oleic acid and ethylene oxide containing about 6 to ethylene oxide units in the molecule. Other nonionic wetting agents, like polyalkylene oxide polymers, commercially known as Pluronics can be used. Partial esters of the above acids with polyhydric alcohols such as glycerol, polyglycerol, sorbitol, or mannitol can also be used.

Suitable anionic wetting agents include the alkali metal salts, preferably sodium salts, of sulfuric acid esters or sulfonic acids containing at least 10 carbon atoms in a molecule, for example, the sodium secondary alkyl sulfates, dialkyl sodium sulfosuccinate available under the registered trademark Teepol, sodium salts of sulfonated castor oil, sodium dodecyl benzene sulfonate.

Granulated or pelleted compositions comprising a suitable carrier having the active ingredient incorporated therein are also included in this invention. These can be prepared by impregnating a granular carrier with a solution of the inert ingredient or by granulating a mixture of a finely divided solid carrier and the active ingredient. The carrier used can consist of or contain a fertilizer or fertilizer mixture, as for example, a superphosphate.

The compositions of this invention can also be formulated as solutions of the active ingredient in an organic solvent or mixture of solvents, such as for example alcohols; ketones, especially acetone; ethers; hydrocarbons; etc.

Where the toxicant itself is a liquid these materials can be sprayed on crops or insects without further dilution.

Petroleum hydrocarbon fractions used as solvents should preferably have a flash point above 73 R, an example of this being a refined aromatic extract of kerosene. Auxiliary solvents such as alcohols, ketones, and polyalkylene glycol ethers and esters can be used in conjunction with these petroleum solvents.

Compositions of the present invention can also be formulated as emulsifiable concentrates which are concentrated solutions or dispersion of the active ingredient in an organic liquid, preferably a water-insoluble organic liquid, containing an added emulsifying agent. These concentrates can also contain a proportion of water, for example, up to about by volume, based on the total composition, to facilitate subsequent dilution with water. Suitable organic liquids include, e.g., the above petroleum hydrocarbon fractions previously described.

The emulsifying agent can be of the type producing water-in-oil type emulsions which are suitable for application by low volume spraying, or an emulsifier of the type producing oil-in-water emulsions can be used, producing concentrates which can be diluted with relatively large volumes of water for application by high volume spraying or relatively small volumes of water for low volume spraying. In such emulsions, the active ingredient is preferably in a non-aqueous phase.

The present invention is further illustrated in greater detail by the following examples, but it is to be understood that the present invention in its broadest aspects, is not necessarily limited in terms of the reactants, or specific temperatures, residence times, separation techniques and other process conditions, etc.; or dosage level, exposure times, test plants used, etc., by which the compounds and/or compositions described and claimed are prepared and/ or used.

EXAMPLE 1 Preparation of N-cyclopropylmethyl-N-n-propyl-4- trifluoromethyl-2,6-dinitroaniline 3,5-dinitro-4-chlorobenzotrifluoride (14.6 grams, 0.054 mole) and N-cyclopropylmethyl-N-n-propylamine (13.0

grams, 0.115 mole) were mixed in a reaction flask, whereupon an exothermic reaction occurred with the temperature rising to a maximum of C. The resultant deep orange-colored reaction mixture was heated at to C. for two hours with occasional stirring. After cooling the mixture, ether was added and the insoluble byproduct, the amine hydrochloride, was removed by filtration. The filtrate was washed with 60 ml. portions of 5% hydrochloric acid and water, and then dried with K CO The ether was removed under vacuum, leaving the red, oily residue of N-cyclopropylmethyl-N-n-propyl 4 trifluoromethyl-2,6-dinitroaniline (14.4 grams). The material was then crystallized by dissolving in hexane and chilling the solution with stirring in a Dry-Ice bath. The resulting bright yellow solids which were obtained upon filtering melted at 2728 C. Elemental analysis.Calculated (percent): C, 48.43; H, 4.65; N, 12.12. Found (percent): C, 48.22; H, 4.69; N, 12.45. The nuclear magnetic resonance spectrum of this compound was consistent with its proposed structure.

EXAMPLE 2 Preparation of N-cyclopropylmethyl-N-ethyl-4-trifluoromethyl-Z,6-dinitroaniline In a reaction flask was placed 3,5-dinitro-4-chlorobenzotrifluoride (85.4 grams, 0.316 mole) and triethylamine (40.5 grams, 0.40 mole), dissolved in 800 ml. of benzene. The solution was cooled to approximately 10 C. with stirring and N-cyclopropylmethyl-N-ethylamine (35 grams, 0.347 mole), dissolved in 100 ml. of benzene, was added dropwise over 1% hours. The mixture was refluxed for 2 /2 hours and then allowed to cool. Filtration of the solids (amine hydrochloride) gave a redcolored filtrate which was washed with 5% H01 and water. After drying the solution with K 00 the solvent was removed at reduced pressure to yield a yellow solid which was recrystallized from cold hexane. The product obtained was N-cyclopropylmethyl-N-ethyl-4-trifluoromethyl-2,6-dinitroaniline, melting point 32-33 C., in a yield of 80 grams. Elemental analysis.Calculated (percent): C, 46.8; H, 4.23; N, 12.61. Found (percent): C, 47.2; H, 4.93; N, 12.69. The nuclear magnetic resonance spectrum substantiated its proposed structure.

EXAMPLE 3 Preparation of N-cyclopropylmethyl-Nmethyl-4- trifluoromethyl-Z,6-dinitroaniline Addition of an ether solution of 3,5-dinitro-4-chlorobenzotrifluoride (10.7 grams, 0.039 mole) to N-cyclopropylmethyl-N-methylamine (3.84 grams, 0.045 mole) and triethylamine (4.95 grams, 0.056 mole), dissolved in ether, yielded a precipitate of amine hydrochloride. The mixture was heated at reflux for one hour, cooled, and filtered. The filtrate, after workup in the usual manner, yielded yellow-orange solids, in a yield of 11.9 grams. The product was recrystallized from petroleum ether and had a melting point range. of 59-60 C. Elemental analysis.Calculated (percent): C, 45.2; H, 3.78; N, 13.1. Found (percent): C, 44.8; H, 4.19; N, 13.3.

EXAMPLE 4 Preparation of N-cyclopropylmethyl-N-ispropyl-4-trifluoromethyl-Z,6-dinitroaniline Following the general procedure of Example 1, N-cyclopropylmethyl-N-isopropyl-amine (13 grams, 0.115 mole) was reacted with 3.5-dinitro-4-chlorobenzotrifluoride (14.6 grams, 0.054 mole) to yield 12.5 grams of product, after recrystallization from hexane. The material melted at 425435 C. Elemental analysis.Calculated (percent): C, 48.43; H, 4.65; N, 12.12. Found (percent): C, 49.02; H, 4.79; N. 12.14.

9 EXAMPLE Preparation of N-cyclopropylmethyl-N-n-butyl-4-trifluoromethyl-2,6-dinitroaniline According to the general procedure of Example 1, N- cyclopropylmethyl-N-n-butylamine (15.0 grams, 0.118 mole) was reacted with 3,5-dinitro-4-chlorobenzotrifluoride (14.6 grams, 0.54 mole) to yield the product, which was recrystallized from hexane and had a melting point range of 30.32 C. Elemental analysis.Calculated (percent): C, 49.9; H, 5.03; N, 11.64. Found (percent): C, 50.08; H, 5.21; N, 11.68.

EXAMPLE 6 Preparation of N,N-bis(cyclopropylmethyl-4-trifluoromethyl-2,6-dinitroaniline Following the general procedure of Example 1, N,N-bis (cyclopropylmethyl)amine (9.0 grams, 0.071 mole) was reacted with 3,5-dinitro-4-chlorobenzotrifluoride (9.73 grams, 0.036 mole) to yield 12.5 grams of crude product. Recrystallization of this material from hexane gave a product having a melting point range of 6162 C. Elemental analysis.Calculated (percent): C, 50.1; H, 4.49; N, 11.70. Found (percent): C, 50.05; H, 4.72; N, 11.36.

EXAMPLE 7 Preparation of 4-(methylsulfonyl)-2,6-dinitro-N- cyclopropylmethyl-N-methylaniline To a suspension of 4-chloro-3,5-dinitrophenyl methylsulfone (7.5 grams, 0.027 mole) in 60 ml. of methanol was added N-cyclopropylmethyl-N-methylamine (5.1 grams, 0.06 mole) dissolved in twice its volume of methanol over a period of minutes. A slight exothermic reaction was noted as orange-yellow colored solids formed during the addition. The mixture was heated at reflux for approximately one hour, chilled to 0 C., and then filtered. This process effected the separation of the methanol-insoluble product from the methanol-soluble amine hydrochloride byproduct. The golden crystalline product (8.4 grams) was recrystallized from hot methanol. The melting point range of this final product was 143-145 C. Elemental analysis.Calculated (percent): C, 43.8; H, 4.59. Found (percent): C, 44.1; H, 4.82.

EXAMPLE 8 Preparation of 4-(methylsulfonyl) -2,6-dinitro-N- cyclopropylmethyl-N-ethylaniline Following the general procedure of Example 7, N-cyclopropylmethyl-N-ethylamine (5.9 grams, 0.06 mole) was reacted with 4-chloro-3,5-dinitrophenyl methylsulfone (7.5 grams, 0.027 mole) to give a crystalline product melting at l10-111 C. after recrystallization from methanol. Elemental analysis.Calculated (percent): C, 45.4; H, 4.98. Found (percent): C, 45.7; H, 5.31.

EXAMPLE 9 Preparation of 4-(methylsulfony1)-2,6-dinitro-N- cyclopropylmethyl-N-n-propylaniline Following the procedure of Example 7, N-cyclopropylmethyl-N-n-propylamine (7.1 grams, 0.06 mole) was reacted with 4-chloro-3,S-dinitrophenyl methylsulfone (7.5 grams, 0.027 mole) to yield a product melting at 132-33 C. Elemental analysis.Caculated (percent): C, 47.1; H, 5.36; N, 8.97. Found (percent): C, 46.9; H, 5.54; N, 8.96.

EXAMPLE 10 Preparation of 4-(methylsulfonyl)-2,6-dinitro-N- cyclopropylmethyl-N-n-butylaniline According to the general procedure of Example 7, N- cyclopropylmethyl-N-n-butylamine (8.0 grams, 0.06 mole) was reacted with 4-chloro-3,S-dinitrophenyl methylsulfone to give a product melting at 88-90 C. Elemental analysis.Calculated (percent): C, 48.5; H, 5.69; N, 8.63. Found (percent): C, 48.0; H, 5.58; N, 8.59.

10 EXAMPLE 11 Preparation of N-cyclopropylmethyl-N-n-propyl-2,6- dinitroaniline In a suitable reaction flask was placed 1-chloro-2,6- dinitrobenzene (10.1 grams, 0.05 mole), triethylamine (7.1 grams, 0.07 mole, 9.7 ml.), and benzene (100 ml.). To this stirred solution, N-cyclopropylmethyl-N-n-propylamine (6.8 grams, 0.06 mole), dissolved in 10ml. of benzene, was added dropwise at room temperature. The resulting solution was refluxed for 15 hours. After cooling the solution and filtering ofl the amine hydrochloride, the filtrate was washed with 9% HCl, then with water, and finally dried with MgSO Removal of the solvent under reduced pressure yielded a viscous red oil which soon crystallized to a yellow solid weighing 12.7 grams. Recrystallization from a heptane-petroleum ether mixture gave a product melting at 47-48 C. Elemental analysis.- Calculated (percent): C, 55.9; H, 6.14; N, 15.05. Found (percent): C, 56.0; H, 6.33; N, 14.79.

EXAMPLE 12 Preparation of N-cyclopropylmethyl-N-n-propyl-Z,6- dinitro-p-toluidine Following the general procedure of Example 1, N-cyclopropylmethyl-N-n-propylamine (11.3 grams, 0.10 mole) was reacted with 3,5-dinitro-4-chlorotoluene (10.8 grams, 0.05 mole) to yield a product melting at 26-28 C. after the usual workup and recrystallization from hexane. Elemental analysis.Calculated (percent): N, 14.33. Found (percent): N, 14.68.

EXAMPLE 13 Preparation of N-cyclopropy1rnethyl-N-n-propyl-4- cyano-2,6-dinitroaniline N-cyclopropylmethyl N-n-propylamine (11.1 grams, 0.098 mole) was dissolved in 100 ml. of benzene. To this stirred solution was added a solution of 4-chloro-3,5-dinitrobenzonitrile (10 grams, 0.044 mole) dropwise over a period of /2 hour. The resulting solution was refluxed for 40 hours. Workup of the product in the usual manner gave a bright yellow solid melting at 1065-108 C. Elemental analysis-Calculated (percent): C, 55.25; H, 5.30; N, 18.41. Found (percent): C, 55.22; H, 5.48; N, 18.07.

EXAMPLE 14 Preparation of N-cyclopropylmethyl-4-trifluoromethyl- 2,6-dinitroaniline Cyclopropylmethylamine hydrochloride (5.3 grams, 0.05 mole), prepared according to the procedure of Roberts and Mazur (JACS 73, pp. 2509-20, 1951), was dissolved in 20 ml. of Water. A solution of 4.0 grams (0.1 mole) of sodium hydroxide was added, followed by a portion-wise addition of solid 3,5-dinitro-4-chlorobenzotrifluoride. The resulting mixture was refluxed for one hour. After cooling, the oily product was seperated from the aqueous phase and dissolved in boiling methanol. Chilling of the alcoholic solution precipitated solids which were filtered and air dried, and had a melting point range of 91 C. Elemental analysis-Calculated (percent): C, 43.5; H, 3.3; N, 13.8. Found (percent): C, 43.3; H, 3.6; N, 13.7.

EXAMPLE 15 Preparation of N-cyclopropylmethyl-N-n-propyl-2-nitro- 4-trifluoromethylaniline According to the general procedure of Example 2, N- cyclopropylmethyl-N-n-propylamine (6.79 grams, 0.06 mole) was reacted with 4-chloro-3-nitrobenzotrifluoride (11.3 grams, 0.05 mole), using benzene as a solvent. The reflux time was extended to 21 hours. Workup of the reaction mixture in the usual way yielded a red oil, which when subjected to vacuum distillation, gave a main cut 1 l (7.0 grams) of red oil having a boiling point range of 143-145 C. at 0.5 mm. of pressure. Elemental analysis.- Calculated (percent): N, 9.27. Found (percent): N, 9.75.

EXAMPLE 16 According to the general procedures outlined in the preceding examples, the following additional compounds were synthesized:

(a) N-cyclopropylmethyl-N-ethyl-2,6-dinitroaniline, M.P.

47.5-49 C. Elemental analysis.Calculated (percent): C, 54.33; H, 5.7; N, 15.84. Found (percent): C, 54.53;H, 6.09;N, 15.59.

(b) N-cyclopropylmetyhl-N-ethyl-2,6-dinitro-p-toluidine,

M.P. 4446 C. Elemental analysis.Calculated (percent): C, 55.90; H, 6.14; N, 15.05. Found (percent): C, 55.83; H, 6.54; N, 15.14.

(c) N cyclopropylmethyl-N-(3-methylmercaptopropyl)- 4-trifluoromethyl-2,6 dinitroaniline, M.P. 36-38 C. Elemental analysis.Calculated (percent): C, 46.0; H, 4.61; N, 10.7. Found (percent): C, 45.75; H, 4.40; N, 10.66.

(d) 4- (methylsulfonyl) -2,6-dinitro-N-cyclopropylmethyl- N-(3-methylmercaptopropyl)aniline, M.P. 7276 C. Elemental analysis.Calculated (percent): N, 10.4. Found (percent): N, 9.58.

(e) N cyclopropylmethyl N-ethyl-4-cyano-2,6-dinitroaniline, M.P.93-94 C. Elemental analysis.-Calculated (percent): N, 19.3. Found (percent): N, 19.39.

(f) N cyclobutylmethyl N-ethyl-4-trifluoromethyl-2,6-

dinitroaniline (oil). Elemental analysis.Calculated (percent): N, 12.1. Found (percent): N, 11.83.

(g) N cyclopentylmethyl-N-ethyl-4-trifluoromethyl-2,6-

dinitroaniline, M.P. 60-62 C. Elemental analysis. Calculated (percent): N, 11.6. Found (percent): N, 11.36.

(h) 4-(methylsulfonyl)-2,6-dinitro-N-cyclopentyl-methyl- N-ethylaniline, M.P. 11912 C. Elemental analysis.- Calculated (percent): C, 48.6; H, 5.69; N, 11.32. Found (percent): C, 48.3; H, 5.40; N, 11.32.

(i) N cyclohexylmethyl-N-methyl-4-trifiuoromethyl-2,6- dinitroaniline, M.P. 104-106" C. Elemental analysis.- Calculated (percent): N, 11.8. Found (percent): N, 11.96.

(j) N cyclopropyl-N-ethyl-4-trifluoromethyl-2,6-dinitroaniline, M.P. 7173 C. Elemental analysis-Calculated (percent): C, 45.2; H, 3.79; N, 13.15. Found (percent): C, 45.16; H, 3.65; N, 13.34.

(k) 4-(methylsulfonyl) 2,6 dinitro-N-cyclopropyl-N- ethylaniline, M.P. 170-171 C. Elemental analysis. Calculated (percent): 43.8; H, 4.59; N, 12.78. Found (percent): C, 43.99; H, 4.96; N, 12.81.

(1) N cyclopropyl N cyclopropylmethyl-4-trifluoromethyl-2,6-dinitroaniline, M.P. 4554 C. Elemental analysis.Calculated (percent): N, 12.2. Found (percent): N, 12.23.

(m) N-cyclohexyl-N-methyl 4 trifluoromethyl 2,6-

dinitroaniline, M.P. 6768 C. Elemental analysis. Calculated (percent) C, 48.5; H, 4.66; N, 12.1. Found (percent): C, 48.67; H, 4.77; N, 11.74.

EXAM'PLE 17 The amines used in the preparation of the compounds mentioned in Examples 1-15 and Examples 16(a)l6(i) can be synthesized via a two-step process, in accordance with the following experimental procedure.

First step A molar quantity of cycloalkanecarboxylic acid chloride is reacted with a 2-molar quantity of an appropriate amine to form the corresponding N-alkylcycloalkanecarboxamide. The HCl liberated during this reaction is captured in the reaction medium by the excess amine via formation of the amine hydrochloride salt. If a suitable organic solvent such as diethylether, benzene, carbon tetra- 12 chloride, etc. is used for the reaction medium, the amine hydrochloride salt, which is insoluble, can be removed by filtration. The amide can then be recovered by removal of the solvent.

Second step The N-alkylcycloalkanecarboxamide product of the first step is reduced with lithium aluminum hydride to the corresponding N-cycloalkylmethyl-N-alkylamine.

Both infrared and nuclear magnetic resonance spectroscopy can be utilized to substantiate the presence of the cyclopropane ring which is contained in many of these compounds.

The following synthetic procedures, described in Examples 18 and 19, illustrate the general mode of preparation of the intermediate amides and amines. The physical constants of these compounds are consolidated in the table which follows, Table II.

EXAMPLE 18 Preparation of N-n-propylcyclopropanecarboxamide In 600 ml. of benzene was dissolved n-propylamine grams, 2.2 moles, 181 ml.). This well-stirred solution was cooled to about 10 C., and a solution of cyclopropanecarboxylic acid chloride (104.5 grams, 1.0 mole) in 100 ml. of benzene was added dropwise over a period of 1% hours. During this time, white solids formed in the reaction medium. The mixture was heated at reflux for about 3 hours, cooled to room temperature, and filtered to remove the insoluble white n-propylamine hydrochloride salt. The filtrate was washed successively with ml. portions of Water 5% HCl, water, 10% NaHCO and Water. The solution after being dried with anhydrous MgSO, was stripped of solvent to yield a crude oil (108.6 grams) which crystallized to a solid upon standing. A sample was recrystallized from petroleum ether at subzero temperatures to give material melting at 34-35" C. Elemental analysis.Calculated (percent): N, 11.01. Found (percent): N, 10.92.

EXAMPLE 19 Preparation of N-cyclopropylmethyl-N-n-propylamine In a reaction flask Was placed a suspension of lithium aluminum hydride (30 grams, 0.786 mole) in anhydrous ether (1 liter). A nitrogen blanket was held over the mixture throughout the reaction. To the stirred mixture was added dropwise a solution of N-n-propyl-cyclopropanecarboxamide (50 grams, 0.393 mole) in 300 ml. of dry ether over a period of two hours. Gentle refluxing of the solvent was evident during the addition. After the addition was complete, the mixture was heated at reflux for approximately 10 hours. The solution was cooled with an ice bath, while 6% aqueous sodium hydroxide was cautiously added dropwise to destroy the unreacted lithium aluminum hydride. The resulting white aluminate salts were removed by filtration and the clear ethereal filtrate was dried with potassium hydroxide pellets. After the ether was removed by distillation, the N-cyclopropylmethyl N n propylamine was distilled at atmospheric pressure and found to have a boiling point range of 136 138 C. The yield was 27 grams. Elemental alysis.- Calculated (percent): N, 11.01. Found (percent): N, 10.97.

As an alternate workup procedure, the ethereal solution obtained after filtration was extracted two or three times with 10% HCl. The acidic aqueous solution was basified with excess aqueous sodium hydroxide, and the amine which formed an insoluble upper layer was extracted with ether. After drying the ether solution with KOH pellets, the distillation procedure as described above was carried out.

Exemplary of products prepared in accordance with the procedures set forth in Examples 17-19 above, are those listed in Table II below.

TABLE II N-alkylcycloalkanecarboxamides V Neycloalkyhnethyl-N-alkylamines R1 CONHR; R CHzNHRz Nitrogen analysis Nitrogen analysis R R2 M.P., 0. Found Calculated B.P., C./1 atm. Found Calculated OH; W 7 48-51 13. 99 14.1 3 91-93. 16. 85 161 4 onion; (oil) 11.81 12. 39 110-12 13. 39 14.12

l n-C H 34-35 10. 92 11. 01 136-38 12. 40 12. 3

l-CrH 91-92 10. 87 11. 01 125 12. 05 12. 3

D- n-C Ho 36-37 9. 98 9. 92 158-59 11. 06 11.0

l 56-58 10.15 10.06 168-72 10.92 11. 1 OH;

, (CHrhSCH; 48-50 8. 09 8. 09 62-3/0.1 mm. 8. 65 8. 82

onion: 136

'l CHgOH: 164-165. 5 10. 51 11.01

NOTE.NMR spectroscopy was used to verify the structures indicated in this table.

EXAMPLE EXAMPLE 21 N-cyclopropyl-N-alkylamines which are used in the preparation of compounds illustrated by Example 16(j), 16(k) and 16(1) may be synthesized by reduction of the corresponding N-cyclopropyl amides under mild conditions. The method of Brown and Heim (see JACS 86, 3566, 1964) utilizing diborane as the reducing agent, can be used to prepare these amines. The following synthesis shows the general technique.

N-cyclopropyl-N-ethylamine In a flask was placed 338 ml. of a 1 M borane in tetrahydrofuran solution (nitrogen atmosphere). The solution was cooled to approximately 0 C., and a solution of N-cyclopropyl-acetamide (16.6 grams, 0.169 mole) in tetrahydrofuran was added dropwise with stirring over a period of 60 minutes, maintaining a temperature of 0- 5 C. The solution was heated at reflux for three hours and then cooled to room temperature. About 90 ml. of 5 N HCl solution was added dropwise and the reaction mixture was heated to reflux for minutes. The tetrahydrofuran was removed by distillation at atmospheric pressure and the residue was made basic with excess NaOH solution. This basic solution was extracted with ether and the extracts were dried over KOH pellets. Distillation afforded 7.2 grams of N-cyclopropyl- -ethylamine boiling at 101103/1 atm. The structure was confirmed by its nuclear magnetic resonance spectrum.

' uated for pro-emergence herbicidal activity in this example. The test procedure employed was as follows:

Two flats seeded with six crops (cotton, soybean, tomato, corn, rice and oats) and six weeds (mustard, morning glory, velvet leaf, crabgrass, Johnson grass, and foxtail) were sprayed with a formulation containing the test chemical at a rate equivalent to 10 lbs/acre. The test chemicals were sprayed as acetone solutions or very small particle acetone suspensions onto the test plants. Sprayers were calibrated to deliver a certain volume of liquid and the calculated amount of active ingredient which would give a rate corresponding to the indicated lbs/acre. The flats were then held in the greenhouse and a response rated after 12 days to 16 days. Response was rated by a scale of 0-10. The 0-10 scale is defined as: 0:110 injury; 13 =slight injury; 4-6=moderate injury, plants TABLE III-Continued N I Rr- N02 Preemergence test I Yel- R Rate Morn- .Toh nlow Vel- 1bs./ Soy- Coting Toma- Crabson foxvet Mus- R! R R3 R4 acre Corn bean ton Rice glory to Oats grass grass tail leaf tard -CH CH N CF; 10 1 0 0 0 0 0 0 0 0 0 0 5 l0 1 0 7 2 0 0 1 9 7 7 l 2 Cm N02 1.25 1 2 0 2 0 0 0 3 0 0 0 0 I CH2 C2H5 NO; SO2CH3 10 0 0 0 0 0 0 0 8 5 5 0 0 CH2 OH; NO; $020113 10 1 0 2 0 0 2 0 1 0 0 0 3 O CH N0 SOECHS 1O 0 0 2 1 0 0 2 9 3 1 0 0 EXAMPLE 22 terial Trefian (N,N-di-n-propyl-4-trifluoromethyl-2,6-dini- EXAMPLE 23 In tln's example a pre-emergence herbicide study was carried out to compare the activity of the commercial matroaniline) with that of a specific example disclosed in this invention, namely N-cyclopropylmethyl-N-n-propyl-4-trifluoromethyl-2,6-dinitroaniline. Tests were carried out on a number of crop and weed species and the chemicals were applied to the surface of the soil as well as incorporated into the soil. Observations were made four weeks after the planting date to determine the relative effects on the crops as well as the overall effect on broadleaf weed species and grassy weed species. Ratings were on a 0-10 scale where 0=no effect and 10=comp1ete kill or no emergence. The data is summarized in Table V. The results show that in general the scope of activity of both compounds against weed species is quite similar. However, in addition, the cyclopropyl derivative appears to show some unexpected crop tolerance which exceeds the tolerance of Trefian to these same species.

TABLE IV.-HERBICIDE ACTIVITY Post emergence test I Yel- R Rate Morn- Johm low Vellbs./ Soy- Coting Toma- Crabson foxvet Mus- R; R2 R R4 acre Corn bean ton Rice glory to Oats grass grass tail leaf tard CH OH; NO; OF; 10 2 1 2 2 1 5 5 1 7 5 5 5 l -CH2 C2115 N02 CF: 10 1 3 1 2 1 1 0 1 2 D-o H2 n-C H N 02 o F8 10 7 s s 5 s s 5 9 s s 5 5 CH 1-C3H7 N 02 C F; 10 2 3 3 3 2 2 5 7 6 5 4 2 TABLE IVC0ntinued R\ /R1 N l Post emergence test I Yel- R4 Rate Morn- J 01111- 10w Vellbs./ Soying Toma- Crabson foxvet Mus- R R2 R3 R4 acre Corn bean Rice glory to Oats grass grass tail leaf tard l -c11, 11-01111 N02 013 10 o 1 2 a a s 4 4 5 4 411, 011, N02 cm 10 0 0 1 o 5 o 0 0 a a c11 011235011, N02 01 3 10 o 2 a 2 6 s a 6 1 3 o112 011 N02 $020113 10 1 2 o 1 1 5 5 0 0 a I -cm 0211,, N0 $020113 10 4 2 1 1 o 6 5 2 a o -o112 11-03111 N02 s 02cm 10 a 4 2 6 1 7 4 0 2 o l c112 11-0111, NO; 3020113 10 0 o o o 1 o o o 0 1 011z (OHmSCH; N02 sown, 1o 0 0 1 o 1 o o 0 o 0 012 11-0311, N02 H 10 3 a 2 4 5 7 6 5 5 4 015 0111: N01 H 10 2 6 2 2 6 a 9 5 7 4 9 011, 11-01111 N02 0113 10 a 1 2 3 5 6 7 1 5 a 5 c112 0211, N02 CH; 10 5 a a 2 6 5 a 9 1 2 1 c112 11-03111 N02 GEN 10 0 0 0 0 4 1 5 s 2 o 0 011, 0211, NO: GEN 10 0 o o o 1 4 2 o 2 1 011, 11-03111 11 CF; 10 a 1 a 2 2 0 a 2 2 1 1 413, 11 NO; CF; 10 0 10 2 o 0 0 o o 0 0 c112 c2115 N02 01; 10 0 10 0 1 3 6 7 6 4 1 o -c111 02115 N02 01 3 10 s 0 0 1 s 5 9 s s 2 5 Q 0113 N02 CF; 10 1 1 1 1 1 1 1 2 1 1 2 CH2 c2115 N02 sogcna 10 a o 0 0 s 2 6 1 0 1 o O-cm 0111 N02 sown; 10 2 2 2 1 1 o o o 0 0 0 G- 0113 N04 50201-13 10 0 u 0 u 1 0 0 0 0 u 0 Norm:

C 1? TD N-cyclopropylmethyl-N-n-propyl-4-trifluoromethyl-2,6-dlnitroaniline. B'.L.=Broadleaved weeds. Gr.= Grassy weeds. S Surface application. I=Soil incorporation.

EXAMPLE 24 EXAMPLE 25 A typical Wettable powder concentrate that is diluted to the desired concentration by dispersing it in water has the following composition:

Parts Active ingredient 50 Solid carrier (e.g., attapulgite) 42 Dispersant (monocalciurn salt of polymeric alkylaryl sulfonic acid) Wetting agent (sodium alkyl naphthalene sulfate (Nekal BA-75')) EXAMPLE 26 A liquid concentrate that is diluted in the field with water has the following composition:

Parts Active ingredient 45 Xylene 45 Emulsifier (blend of calcium dodecylbenzenesulfonate and alkyl aryl polyethylene oxide adduct) It should be understood from the foregoing that the above description is merely illustrative of preferred embodiments and specific examples of the present invention and that in all of which embodiments and examples, variations, such as, e.g., those previously described, can be made by those skilled in the art without departing from the spirit and purview thereof, the invention being defined by the following claims.

What is claimed is:

1. Compounds of the formula wherein 1) R is a cycloalkyl containing group characterized by the following structural formula in which the cycloalkyl ring itself may be optionally substituted with C -C alkyl or C -C alkenyl; n is either 0 or 1; m is a positive integer ranging from 2 to 4 when n is 1, however when n is 0, m is 2; (2) R is C -C straight or branched chain alkyl, C -C alkenyl, cyclopropyl, C cycloalkylalkyl or C -C alkylmercaptoalkyl; (3) R is hydrogen or N0 (4) R is hydrogen, C -C alkyl, CF CH S(O) C H S(O) or C H S(O) wherein x is 0,

2. N-cyclopropylmethyl-N-ethyl 4 trifiuoromethyl- 2,6-dinitroaniline.

3. N cyclopropylmethyl-N-n-propyl 4 trifluoromethyl-2,6-dinitroaniline.

4. N-cyclobutylmethyl-N-ethyl 4 trifluoromethyl-Z, 6-dinitroaniline.

5. 'N-cyclopropylmethyl-N-n-propyl 2,6 dinitroaniline.

6. N-cyclopropylmethyl-N-ethyl 2,6 dinitro-p-toluidine.

7. N-cyclopropylmethyl-N-n-propyl 2,6 dinitro-ptoluidine.

8. N,N-bis(cyclopropylmethyl) 4 trifluoromethyl- 2,6-dinitroaniline.

9. 4- (methylsulfonyl) 2,6 dinitro-N-cyclopropylmethyl-N-ethylaniline.

10. 4-(methylsulfonyl) 2,6 dinitro-N-cyclopropylmethyl N-n-butylaniline.

11. N cyclopropyhN-ethyl 4 trifiuoromethyl-2,6- dinitroaniline.

12. N-cyclopropyl-N-cyclopropylmethyl 4 trifluoromethyl-2,6-dinitroaniline.

13. 4-(methylsulfonyl) 2,6 dinitro-N-cyclopropyl- N-ethylaniline.

References Cited UNITED STATES PATENTS 1,836,295 12/1931 Thiess et al. 260577 X 3,111,403 11/1963 Soper 260577 X 3,168,442 2/1965 Brunner et al. 260577 X 3,257,190 6/1966 Soper 260577 X 3,403,180 9/1968 Soper 260 -577 FOREIGN PATENTS 1,253,176 12/1960 France 260577 OTHER REFERENCES Close: Chemical Abstracts, vol. 51 (1957), p. 10454b.

CHARLES B. PARKER, Primary Examiner R. L. RAYMOND, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Nu.

lnventofls) Lester L. Maravetz U h NW V It is certified that error appears in the above-idenLified patent and that said Letters Patent are hereby corrected as shown below:

Column 22, lines 6-8, please cancel ma and replace with H Signed and sealed this 3rd day of December 1974.

(SEAL) Attest:

14:60! 1-1. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

